Lubricating oil composition



Patented Jan. 8, 1963 This invention relates to a novel lubricating oil composition and more particularly pertains to a lubricating oil composition having outstanding deiergency characteristics and corrosion inhibiting propert es.

Many oils are not well suited as lubricants for use in internal combustion engines, particularly of the ty e operating under severe conditions, since under such conditions the lubricants are susceptible to deterioration resulting in the development of carbonaceous and/or resinous or similar varnish-like deposits in the engines and on and about the valves and rings of the engine nd under some conditions such oils are not efiective in .ting corrosion of the various com onents of the engine.

It has heretofore been found that certain hydrolyzed reaction products of a phosphorus sulfide and an olefin hydrocarbon such as an olefin polymer, when small amounts to a hydrocarbon oil, are effective in hibiting the formation of varnish, sludge, carbon and like in lubricating oils during use. It has also been found that neutralizing these hydrolyzed reaction products of a phosphorus sulfide and an olefinic hydrocarbon with a basic reagent having a metal constituent, particularly basic barium compounds, provides a compost .on which is effective as a detergent. While general dificulty is encountered in neutralizing such reaction roducts in the manner heretofore practiced, it has been observed that when neutralizing such reaction products with an amount of basic barium compound which would result in a composition having a metal to phosphorous ratio greater than the amount necessary to form a neutral salt greater than about a lzl mol ratio or 4.45 weig t ratio or barium to phosphorus) d ulties are encountered by reason of the formation of gels which make it pr. ticaily impossible to filter the product to remove u ,ted constit ents. It has also been observed that the elds when e i'iploying such methods are quite low. Moreover, in the manutacture of these lubricants containing the neutralized, metal containing hydrolyzed reaction product of a phosphorus sulfide and an olefinic hydrocarbon, a substantial amount of the sulfur introduced therein by the phosphorus'sultide is lost in the hydrolysis. Consequently, under certain conditions these compositions do not ffectively inhibit corrosion of the metal surfaces which they lubricate. Moreover, when preparing such compositions in accordance with the prior art, it has generally bee necessary to treat the product which has been s to hydrolysis to remove undesirable hydrolysis p This is accomplished, for example, by clay treatment.

As more and more fuels h..ving high sulfur contents come into use, particularly in compression-fi tion engines, i.e., diesel engines, it becomes necessary to provide lubricants which have a high metal to phosphorus ratio providing reserve basicity to disperse p icles of c rbon, resin and the like the lubricating oil. it is well-. vn that increasing the metal content, and hence the basic y, of the additive of the type described herein will efiectively increase the ability of the oil to neutralize acids formed by the combustion of the fuel. it is also known that the most economical way of increasing tilfi metal content of the lubricating oil containing additive of the type de scribed herein is to increase the metal to phosphorus ratio of the additive rather than to increase the total amount of additive in the oil to obtain the desired cont nt It has, however, heretofore been impractical to increase the metal to phosphorus ratio substantially without adversely affecting the filterability of the product.

It is an object of our invention to provide a lubricant for internal combustion engines which will have outstanding detergency characteristics and will also inhibit corrosion of metal surfaces. Another object is to provide a method of neutralizing reaction products of a phosphorus sulfide and an olefinic hydrocarbon with a basic barium compound whereby a bright product, free of gel and having a high barium to phosphorus ratio is obtained. it is a further object of our invention to provide a method of preparing a lubricant additive whereby hydrolysis is prevented and the additional process steps to remove undesirable products formed during such hydrolysis are avoided. These and additional objects will become apparent as the description of the invention proceeds.

We have discovered that a product having the desired detergency characteristics and corrosion inhibiting properties can be obtained by incorporating in a lubricant composition a minor proportion, from about 0.001 percent to about 10 percent by weight, and preferably from about 0.1 percent to about 5 percent by weight of the product obtained by reacting an olefinic hydrocarbon having a molecular weight of from about 150 to about 50,000, particularly an olefinic polymer of butylene, with from about 1 percent to about 50 percent by Weight, and preferably from about 5 percent to about 25 percent by weight of a phosphorus sulfide at a temperature of from about 200 F. to about 600 F, and preferably from about 300 F. to about 500 F; esterifying the phosphorus sulfide olefinic hydrocarbon reaction product with from about 0.25 to about 3.0 mols, and preferably about 1 mol, per mol of phosphorus present in the phosphorus sulfideolefinic hydrocarbon reaction product, of an alkanol having from 1 to about 12 carbon atoms or a phenol having up to about 20 side chain carbon atoms. Methanol is the preferred alkanol and nonyl phenol or phenol per se are preferred phenols. The esterifyng reaction is carried out at a temperature of from about F. to about 350 F. depending upon the hydroxy compound used, for at least about /2 hour and preferably from about 4 to about 6 hours. The esterified product is then saponified with at least about 1 mol, and preferably about 2 mols, of a basic barium compound, preferably barium oxide, per mol of phosphorus in the esterified product at a temperature from about 125 F. to about 350 F. and preferably from about 240 F. to about 300 F. for at least about /2 hour and preferably about 2 hours. The saponified product can then be contacted with carbon dioxide, if desired, to reduce the excess alkalinity of the product. This reaction is carried out at a temperature of from about 125 F. to about 350 F. preferably from about 240 to 300 F. for a period of time up to about 10 hours and preferably not more than about 2 hours. It is essential, in order to avoid undesirable hydrolysis of the product during its preparation, that Water is not admitted to the system. Thus, the preferred basic barium compound is barium oxide, although barium hydroxide can be employed. The use of the various hydrates of basic barium compounds is to be avoided. For the same reason, it is likewise essential that the alkanols or phenols employed in the reaction are nOt contaminated with water, i.e., only anhydrous alkanols or phenols may be employed.

As stated hereinbefore, the preferred alkanols which can be employed are those having up to about 12 carbon atoms. By reason of cost and availability, the lower molecular weight alcohols such as methyl, ethyl and isopropyl are particularly preferred, although butanol, hexanol, heptanol, octanol and their various isomers are Well 1 may be used having up to about 20 side chain carbon atoms, either in one side chain or two or more side chains.

In the preparation of the phosphorus sulfide-olefinic hydrocarbon reaction product, the olefin is reacted with a phosphorus sulfide such as P 8 P 5 P sor other phosphorus sulfides, and preferably phosphorus pentasulfide, P285.

The olefinic hydrocarbon constituent in this reaction is preferably a mono olefin hydrocarbon polymer resulting from the polymerization of low molecular weight mono-olefinic hydrocarbons or iso-mono-olefinic hydrocarbons, such as. propylenes, butylenes and amylenes or the co-polymers obtained by the polymerization of hydrocarbon mixtures containing iso-mono-olefins and monoolefins of less than 6 carbon atoms. The polymers can be obtained by the polymerization of these olefins or mixtures of olefins in the presence of a catalyst such as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel- Crafts type.

Other preferred olefins suitable for the preparation of the hereindescribed phosphorus sulfide reaction products are olefins having at least 20 carbon atoms in the molecule of which from about 13 to about 18 carbon atoms, and preferably at least 15 carbon atoms are in a long chain. Such olefins can be obtained by the dehydrogenation of parafiins, such as by the cracking of paraflin Wax or by the dehalogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated paratfin Waxes.

In general, the preparation of the barium-containing phosphorus sulfide-olefinic hydrocarbon reaction product, in accordance with the present invention, is carried out in the following manner. The olefinic hydrocarbon such as, for example, an olefinic polymer of the desired molecular weight, is reacted with from about 1 percent to about 50 percent, and preferably from about 5 percent to about 25 percent, of a phosphorus sulfide such as P 8 at a temperature of from about 200 F. to about 600 F. in a non-oxidizing atmosphere such as, for example, an atmosphere of nitrogen. The reaction is carried out for from about one to about ten hours or more, and preferably for about 5 hours. The phosphorus sulfide-olefinic hydrocarbon reaction can, if desired, be carried out in the presence of a sulfurizing agent such as elemental sulfuror a halide of sulfur. The reaction product thus obtained is then preferably diluted with a normally liquid hydrocarbon, generally the same as, or similar to, the hydrocarbon oil in which the finished additive is to be employed, to a total phosphorus content of from about 0.5 percent to about 5 percent, and preferably to a phosphorus content of from about 1 percent to about 2 percent.

The phosphorus sulfide-olefinic hydrocarbon reaction product, preferably oil diluted, is then heated to at least about 125 F., depending upon the particular mono-hydroxy compound used, and is esterified with from about 0.25 to about 3.0 mols, and preferably about 1 mol, per mol of phosphorus in the phosphorus sulfide-olefinic hydrocarbon reaction product, of an alkanol having from 1 to about 12 carbon atoms or phenol or an alkylated phenol. The esterification'reaction is carried out for at least about /2 hour and preferably from about 4 to 6 hours. Although the reaction may be continued for as long as hours or more, this is not generally necessary and is uneconomical. Hydrogen sulfide is evolved during the esterification reaction and it can be removed by blowing the reaction mixture with nitrogen; this is not essential, however, but merely tends to speed the reaction. When the esterification reaction has been completed,

which is indicated when hydrogen sulfide no longer evolves, the product is saponified with a basic barium compound such as barium oxide. The amount of barium oxide employed is at least about one mol per mol of phosphorus in the esterifiedproduct. At a 1:1 ratio of barium to phosphorus, a neutral salt will be formed. It is generally preferable, however, and one of the objects of this invention, to form a basic salt having a high barium to phosphorus ratio. Thus, it is preferable to employ from two to three times the amount of basic barium compound as that necessary to form the neutral salt. t a mol ratio of barium to phosphorus of about 2, the efficiency of barium utilization is maximized and is about Basic barium compound in excess of this amount can be employed without deleterious effect but the eificiency of barium utilization will decrease substantially and hinder filtration of the product after the reaction is completed.

After addition of the basic barium compound to the reaction mixture, the temperature is maintained between about F. and 350 F. and preferably between about 240 F. and 300 F. Higher temperatures, of course, increase the reaction rate and are thus desirable. The reaction mixture is thus heated for at least about one-half hour and preferably for about two to about six hours. The reaction may be continued for as long as ten hours or more but this is generally not necessary and is uneconomical. The reaction product can then be filtered in order to remove unreacted components; however, this is not always necessary if the preferred amounts as hereinbefore specified are employed.

After saponification, the product can be blown with carbon dioxide to reduce excess alkalinity. Although not necessary, it is sometimes desirable to do so in order to meet certain specifications and to provide an additive mixture with a very high barium to phosphorus ratio and yet being essentially neutral. The carbon dioxide blowing step is carried out at a temperature in the range of from about 125 F. to about 350 F. and for convenience generally at the temperature at which the prodnot was saponified. Carbon dioxide treating time can vary over wide limits depending upon the degree to which excessive alkalinity is desired to be reduced. Thus the carbon dioxide blow may be carried out for a few minutes, or for as long as 10 hours or more. We have found, however, that contacting with CO for periods longer han about 2 hours has practically negligible effect upon reducing basicity of the product.

The following examples are illustrative of our invention:

EXAMPLE 1 Butylene polymer (of about 700 molecular weight) was reacted with about 15 percent P S at a temperature of 400 F. in an atmosphere of nitrogen for about 5 hours. This reaction product Was then diluted with an SAE 5 base oil to a phosphorus content of 2.0 percent. The reaction mixture was heated to about 180 F. and about two mols of methyl alcohol per mol of phosphorus was added to form the ester. The end of the reaction was noted when alcohol no longer refluxed and also when hydrogen sulfide evolution ended. About two mols of barium oxide per mol of phosphorus present in the ester was then added to the mixture and the temperature was increased to 240 F. and held at that temperature for 3 hours. The product was then filtered. it contained 9.66% barium, 1.59% phosphorus and 1.6% sulfur; giving a barium to phosphorus ratio of about 6:1. The product had an alkalinity of 33.66 mg. KOH/ gr.

EXAMPLE 2 Same as Example 1 except that after saponification with barium oxide, the product was blown with carbon dioxide for 10 minutes. Thi product contained identical amounts of barium, phosphorus and sulfur but the alkalinity was reduced to 5.3 mg. KOH/ gr.

EXAMPLE 3 The diluted butylene polymer-P 8 reaction product of Example 1 was reacted with about one'mol of nonyl phenol per mol of phosphorus present in the foregoing reaction product. The temperature of esterification was held between 270 F. and 300 F. for about 5 hours and the reaction mixture was blown with nitrogen throughout this period. The ester was then saponitied with about 2 mols of barium oxide per mol of phosphorus present in the ester at a temperature between 250260 F. for about 3 hours. The product was then blown with carbon dioxide for an additional 2 hours at the same temperature. The final product contained 8.31% barium, 1.39% phosphorus and 1.66% sulfur; having a barium to phosphorus ratio of about 6:1 and an alkalinity of 2.5 mg. KOH/ gr.

EXAMPLE 4 An additive mixture in accordance with the prior art was prepared as follows. The P S -butylene polymer of Example 1 was hydrolyzed in the presence of steam at a temperature or" about 350 F. This product was then diluted with an SAE 20 base oil to a phosphorus content of 1.5 percent and then contacted with fullers earth at a temperature of about 300 F. and filtered. The hydrolyzed, clay-contacted product was then neutralized with an excess of barium hydroxide octahydrate at a temperature of about 350 F. and then filtered. The product thus obtained had a barium content of 3.04 percent, a phosphorus content of 2.1 percent and less than 0.5 percent sulfur.

EXAMPLE 5 To demonstrate the necessity of first esterifying and then saponifying, this example is presented wherein methanol and barium oxide are added simultaneously. The diluted P S -butylene polymer prepared as described in Example 1 was reacted with about 2 mols of barium oxide (based on phosphorus content of the reaction mixture) in the presence of about 5 mols of methanol (also based on phosphorus content of the reaction mixture) at a temperature of 160-180 F. for about 4 hours. The alcohol was then distilled off at about 300 F. and the product was filtered. It contained 5.31% barium, 1.48% phosphorus and 2.89% sulfur; thus having a barium to phosphorus ratio of only about 3.6, indicating barium oxide utilization of only about 50%. As pointed out above, this example illustrates that esterification prior to saponification is necessary to obtain very high barium to phosphorus ratios.

EXAMPLE 6 Similar to Example except that nonyl phenol was used instead of methanol. The product obtained had a barium to phosphorus ratio of only 4.6 to 1 and was extremely difli'cult to filter. The yield was less than 10% and the product was cloudy.

As pointed out hereinbefore, the compositions provided by our invention, due to their high barium to phosphorus ratio, have superior effectiveness as detergents. This is demonstrated by the results obtained with the so-called conventional L-l test. This test is made on a Caterpillar 1-A-S1 single cylinder Caterpillar engine equipped with new pistons, rings and liners, operating for 480 hours at 100 r.p.m. at a load of 19.8 B.H.P., with an oil sump temperature of 145150 35., and a water outlet temperature of 175-180 F. The fuel employed in this test was at the so-called S-l level, containing 1 percent sulfur. This test is designed to measure oil detergency and inspections are made at 120, 240 and 480 hours. Piston lands, grooves and liner are inspected for carbon and lacquer. Varnish values are based on a visual rating of from 1 to 10 in which a rating of 10 indicates no varnish and a rating of 1 indicates excessive amounts of varnish. The following compositions were subjected to the L-1 test, results of which are shown in Table 1:

3ccase o l 6 Sample C 6.6% of the product of Example 5 93.4% SAE 30 base oil TABLE 1.-L1 ENGINE TESTHIGH SULFUR FUEL The results shown in Table I for Sample A demonstrate the eifectiveness of our compositions as a detergent. Sample B is typical of the commercially available motor oil detergents and it is apparent that our composition is far superior to Sample B. While the commercially available detergents, exemplified by Sample 13 in Table 1 are very effective as regards detergency characteristics, it is necessary to incorporate with them an additional corrosion inhibitor. This is not necessary when using our composition inasmuch as it exhibits excellent corrosion inhibition properties due to its high sulfur content. Sample C which contains the additive of Example 5 which was prepared by saponification in the presence of methanol is demonstrated to be inferior with respect to detergency to our composition which was prepared by first esterifying the product and then saponifying.

While the present invention has been described by the use of our composition in petroleum lubricating oils, other lubricating oil bases may be employed such as hydrocarbon oils, natural or synthetic, such as those obtained by the polymerization of olefins, as well as synthetic lubricating oils of the alkylene oxide types, and the polycarboxylic acid ester type oils such as the oil-soluble esters of adipic acid, sebacic acid, azelaic acid, etc. It is also contemplated that various other of the well known additives, such as anti-oxidants, anti-foaming agents, pour point depressors, extreme pressure agents, anti-wear agents, V.I. improvers, etc. may be incorporated in lubricating oils containing the additive of our invention.

Unless otherwise stated, the percentages stated herein and in the claims are weight percentages.

While we have described our invention by reference to specific embodiments thereof, the same are given by way of illustration. Modifications and variations will be apparent from our description to those skilled in the art.

We claim:

1. A lubricant composition comprising a major proportion of a lubricating oil and in combination therewith a minor proportion, from about 0.001% to about 10% by weight, of a saponified reaction product having a barium to phosphorus content of at least about 6:1 and obtained by reacting under anhydrous conditions an olefinic hydrocarbon having a molecular weight of from about 150 to 50,000 with from about 1% to about 50% by weight of a phosphorus sulfide at a temperature of from about 200 F. to about 600 F., esterifying the phosphorus sulfideolefinic hydrocarbon reaction product with from about 0.25 to about 3.0 moles per mole of phosphorus present in the phosphorus sulfide-olefinic hydrocarbon reaction product of a monohydroxy compound selected from the group consisting of alkanols having from 1 to about 12 carbon atoms and phenols having up to about 20 side chain carbon atoms at a temperature of from about F. to about 300 F. for at least about one-half hour, and saponifying the esterified product with from about 2 to 3 moles of a basic barium compound per mole of phosphorus in said esterified product at a temperature of from about 125 to about 350 F. for at least about one-half hour whereby the resulting product is said saponified reaction product having a barium to phosphorus content of at least about 6:1.

2. A lubricant composition comprising a major proportion of a lubricating oil and in combination therewith a minor proportion, from about 0.001% to about by weight, of the saponified reaction product having a barium to phosphorus ratio of about 6:1 and obtained by reacting under anhydrous conditions an olefinic hydrocarbon having a molecular weight of from about 150 to 50,000 with from about 1% to about 50% by weight of a phosphorus sulfide at a temperature of from about 200 F. to about 600 F., esterifying the phosphorus sulfideolefinic hydrocarbon reaction product with from about 0.25 to about 3.0 moles per mole of phosphorus present in the phosphorus sulfide-olefinic hydrocarbon reaction product of a monohydroxy compound selected from the group consisting of alkanols having from 1 to about 12 carbon atoms and phenols having up to about side chain carbon atoms at a temperature of from about 125 F. to about 300 F. for about one-half hour, and saponifying the esterified product with from about 2 to 3 moles of a basic barium compound per mole of phosphorus in said esterified product at a temperature of from about 125 to about 350 F. for about one-half hour whereby the resulting product is said saponified reaction product having a barium to phosphorus content of about 6: 1.

3. The lubricant composition of claim 1 wherein said saponified reaction product is contacted with carbon dioxide at a temperature in the range of from about 125 F. to about 350 F.

4. The lubricant composition of claim 1 wherein said olefinic hydrocarbon is a polymer of butylene.

5. The lubricant composition of claim 1 wherein said phosphorus sulfide is phosphorus pentasulfide.

6. The lubricant composition of claim 1 wherein said basic barium compound is barium oxide.

7. The lubricant composition of claim 1 wherein said mono-hydroxy compound is methanol.

8. The lubricant composition of claim 1 wherein said mono-hydroxy compound is nonyl phenol.

9. A lubricant composition comprising a major proportion of a lubricating oil and in combination therewith a minor proportion, from about 0.001% to about 10% by weight, of the product obtained by reacting under anhydrous conditions a butylene polymer having a molecular weight of from about 150 to about 50,000 with from about 1% to about 50% by weight of phosphorus pentasulfide at a temperature of from about 200 F. to about 600 F., esterifying the phosphorus pentasulfide-butylene polymer reaction product with from about 0.25 to about 3.0 mols per mol of phosphorus present in the phosphorus pentasulfide-butylene polymer reaction product of a monohydroxy compound selected from the group consisting of alkanols having from 1 to about 12 carbon atoms and phenols having up to about 20 side chain carbon atoms at a temperature of from about F. to about 350 F. for at least about A2 hours, saponifying the esterified product with from about 2 to about 3 mols of barium oxide per mol of phosphorus in said esterifiedproduct at a temperature of from about 125 F. to about 350 F. for at least about /2 hour, and contacting the saponified reaction product with carbon dioxide at a temperature of from about 125 F. to about 350 F.

10. The method of preparing a phosphorus, sulfur and barium containing lubricating oil additive having a high barium to phosphorus ratio and sufiicient sulfur to effectively inhibit corrosion of metal surfaces which method comprises reacting under anhydrous conditions an olefinic hydrocarbon having a molecular weight of from about to about 50,000 with from about 1% to about 50% by Weight of a phosphorus sulfide at a temperature of from about 200 F. to about 600 F., esterifying the phosphorus sulfide-olefinic hydrocarbon reaction product with from about 0.25 to about 3.0 mols per mol of phosphorus present in the phosphorus sulfide-olefinic hydrocarbon reaction product of a mono-hydroxy compound selected from the group consisting of alkanols having from 1 to about 12 carbon atoms and phenols having up to about 20 side chain carbon atoms at a temperature of from about 125 F to about 350 F. for at least about /2 hour and saponifying the esterified product with from about 2 to about 3 mols of a basic barium compound per mol of phosphorus in the esterified product at a temperature of from about 125 F. to about 350 F. for at least about /2 hour.

11. The method of claim 10 wherein said saponified product is contacted with carbon dioxide at a temperature in the range of from about 125 F. to about 350 F.

12. The method of claim 10 wherein said olefinic hydrocarbon is a polymer of butylene.

13. The method of claim 10 wherein said phosphorus sulfide is phosphorus pentasulfide.

14. The method of claim 10 wherein said basic barium compound is barium oxide. 15. The method of claim 10 wherein said mono-hydroxy compound is methanol.

16. The method of claim 10 wherein said mono-hydroxy compound is nonyl phenol.

References Qited in the file of this patent UNITED STATES PATENTS 2,409,878 May Oct. 22, 1946 2,461,961 Buckmann et al. Feb. 15, 1949 2,767,164 Assert et al. Oct. 16, 1956 2,806,022 Sabol Sept. 10, 1957 2,851,416 Sabol et al. Sept. 9, 1958 

1. A LUBRICANT COMPOSITION COMPRISING A MAJOR PROPORTION OF A LUBRICATING OIL AND IN COMBINATION THEREWITH A MINOR PROPORTION, FROM ABOUT 0.001% TO ABOUT 10% BY WEIGHT, OF A SAPONIFIED REACTION PRODUCT HAVING A BARIUM TO PHOSPHORUS CONTENT OF AT LEAST ABOUT 6:1 AND OBTAINED BY REACTING UNDER ANHYDROUS CONDITIONS AN OLEFINIC HYDROCARBON HAVING A MOLECULAR WEIGHT OF FROM ABOUT 150 TO 50,000 WITH FROM ABOUT 1% TO ABOUT 50% BY WEIGHT OF A PHOSPHORUS SULFIDE AT A TEMPERATURE OF FROM ABOUT 200* F. TO ABOUT 600*F., ESTERIFYING THE PHOSPHORUS SULFIDEOLEFINIC HYDROCARBON REACTION PRODUCT WITH FROM ABOUT 0.25 TO ABOUT 3.0 MOLES PER MOLE OF PHOSPHORUS PRESENT I3IN THE PHOSPHORUS SULFIDE-OLEFINIC HYDROCARBON REACTION PRODUCT OF A MONOHYDROXY COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKANOLS HAVING FROM 1 TO ABOUT 12 CARBON ATOMS AND PHENOLS HAVING UP TO ABOUT 20 SIDE CHAIN CARBON ATOMS AT A TEMPERATURE OF FROM ABOUT 125*F. TO ABOUT 300*F. FOR AT LEAST ABOUT ONE-HALF HOUR, AND SAPONIFYING THE ESTERIFIED PRODUCT WITH FROM ABOUT 2 TO 3 MOLES OF A BASIC BARIUM COMPOUND PER MOLE OF PHOSPHORUS IN SAID ESTERIFIED PRODUCT AT A TEMPERATURE OF FROM ABOUT 125 TO ABOUT 350*F. FOR AT LEAST ABOUT ONE-HALF HOUR WHEREBY THE RESULTING PRODUCT IS SAID SAPONIFIED REACTION PRODUCT HAVING A BARIUM TO PHOSPHORUS CONTENT OF AT LEAST ABOUT 6:1. 